Covalently attached ionophores extend the working range of potentiometric pH sensors with poly(decyl methacrylate) sensing membranes

The pH working range of solid-contact ion-selective electrodes (ISEs) with plasticizer-free poly(decyl methacrylate) sensing membranes is shown to be expanded by covalent attachment of H⁺ ionophores to the polymeric membrane matrix. In situ photopolymerization not only incorporates the ionophores into the polymer backbone, but at the same time also attaches the sensing membranes covalently to the underlying inert polymer and nanographite solid contact, minimizing sensor drift and preventing failure by membrane delamination. A new pyridine-based H⁺ ionophore, 3-(pyridine-3-yl)propyl methacrylate, has lower basicity than trialkylamine ionophores and expands the upper detection limit. This reduces in particular the interference from hydrogen phthalate, which is a common component of commercial pH buffers. Moreover, the lower detection limit is improved by replacing the CH₂CH₂ spacer of previously reported dialkylaminoethyl methacrylates with a (CH₂)₁₀ spacer, which increases its basicity. Notably, for the more basic and highly cation-selective ionophore 10-(diisopropylamino)decyl methacrylate, the extent of counterion interference from hydrogen phthalate shifted the upper detection limit to lower pH by nearly one pH unit when the crosslinker concentration was decreased.